CN117819541A - Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method - Google Patents
Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method Download PDFInfo
- Publication number
- CN117819541A CN117819541A CN202410238826.5A CN202410238826A CN117819541A CN 117819541 A CN117819541 A CN 117819541A CN 202410238826 A CN202410238826 A CN 202410238826A CN 117819541 A CN117819541 A CN 117819541A
- Authority
- CN
- China
- Prior art keywords
- graphite
- leaching
- acid
- temperature
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000010439 graphite Substances 0.000 title claims abstract description 111
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 111
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000002994 raw material Substances 0.000 title claims abstract description 32
- 238000002386 leaching Methods 0.000 claims abstract description 126
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 66
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012141 concentrate Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 38
- 238000001035 drying Methods 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 230000007935 neutral effect Effects 0.000 claims abstract description 21
- 238000000746 purification Methods 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000012216 screening Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000007493 shaping process Methods 0.000 claims abstract description 12
- 238000005188 flotation Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011148 porous material Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 description 27
- 239000003513 alkali Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 17
- 239000002585 base Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000007873 sieving Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002180 crystalline carbon material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The application provides a method for purifying graphite by a raw material high-temperature drying-free simple acid-base method to realize high yield, and relates to the technical field of graphite purification. The method comprises the following steps: mixing graphite concentrate with concentrated sulfuric acid, and roasting at a low temperature to obtain sulfuric acid curing material; mixing the sulfuric acid curing material with hydrochloric acid, leaching, performing solid-liquid separation to obtain an acid leaching sample, and washing the acid leaching sample to be neutral to obtain a solid to be treated; carrying out first screening treatment on solid to be treated, wherein the oversize is a high-carbon graphite product with a fixed carbon content of 94% -98%, and carrying out fine grinding, shaping and purification on the undersize to obtain high-purity spherical graphite; or, carrying out alkaline leaching on the solid to be treated, carrying out solid-liquid separation to obtain an alkaline leaching sample, washing the alkaline leaching sample to be neutral, then carrying out second screening treatment, wherein the oversize product is a high-purity graphite product, and carrying out fine grinding, shaping and purification on the undersize product to obtain the high-purity spherical graphite. According to the method provided by the application, high-temperature drying is not needed for the graphite concentrate after flotation, and high yield of the oversize products can be achieved through a simple acid-base method.
Description
Technical Field
The application relates to the technical field of graphite purification, in particular to a method for purifying graphite by using a simple acid-base method and adopting a raw material free of high-temperature drying mode.
Background
Graphite is a high-energy crystalline carbon material, and has higher application value in high-performance materials due to the unique structure, the characteristics of electric conduction, heat conduction, lubrication, high temperature resistance, stable chemical properties and the like, and is widely applied to the fields of metallurgy, machinery, environmental protection, chemical industry, fire resistance, new energy, nuclear energy, electronics, medicine, military industry, aerospace and the like, and becomes an indispensable nonmetallic material for modern industry and development of high, new and sharp technologies, and the position in economic development is more and more important.
The graphite purifying method mainly comprises a flotation method, an acid-base method, a hydrofluoric acid method, a chloridizing roasting method and a high-temperature purifying method. These five methods can be classified into physical purification methods (flotation method and high temperature purification method) and chemical purification methods (acid-base method, hydrofluoric acid method, chlorroasting method).
Li Songhe et al disclose in the patent "a graphite purification process and graphite" (CN 114212788 a), the purification process comprising the steps of: mixing a graphite raw material with a hydrochloric acid solution for first acid treatment, and washing with water to obtain a first intermediate material in the first step; mixing the first intermediate material with an alkali solution and roasting to obtain a roasting material; adding the roasting material into a reaction kettle, and performing second-step water washing under the conditions of mechanical stirring and ultrasonic vibration until the roasting material is neutral to obtain a second intermediate material; and mixing the second intermediate with hydrochloric acid solution for the second acid treatment, washing with water in the third step, and drying to obtain graphite.
Zhang Tao et al disclose in the patent "a graphite high-efficiency alkali acid process purification system and process" (CN 115490230 a), a purification system comprising a raw material mixing unit, a graphite alkali fusion unit and a chemical purification/washing/dehydration unit, which are sequentially connected.
Wenqing et al disclose in patent 'a decompression alkali fusion graphite purification method' (CN 116040626A), the decompression alkali fusion method is utilized to strengthen the common alkali fusion process, improve the permeation and diffusion of reaction liquid in the graphite layer and the micropores in the graphite, permeate high-concentration sodium hydroxide in the graphite, improve the impurity removal effect, solve the problems of uneven mixing of common alkali fusion alkali liquid and the graphite and insufficient reaction with impurities in the graphite, and finally purify the graphite, wherein the fixed carbon content of the finally purified graphite is more than or equal to 99.9%.
The above patents are all improvements of the traditional alkali roasting/acid leaching process, and have the problems of high energy consumption, easy corrosion of equipment by alkali and the like.
In addition, in the prior acid-base purification technology, the raw materials for graphite purification are generally graphite raw ores, after flotation, as the beneficiation reagent is an organic matter and the dosage is hundreds times or more than that of common minerals, the raw materials are dried under the high temperature condition of about 500 ℃, and the aim is that: 1. volatile is reduced; 2. the influence of a flotation reagent on leaching by the current industrial hydrofluoric acid method is reduced; 3. and (5) drying. However, such an operation greatly increases the energy consumption of production and increases the production cost.
At present, how to simply and effectively purify graphite, reduce energy consumption and improve economic benefit is a problem worthy of research.
Disclosure of Invention
The purpose of the application is to provide a method for purifying graphite by using a simple acid-base method to realize high yield without high-temperature drying of raw materials, so as to solve the problems.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a method for purifying graphite by a raw material high-temperature drying-free simple acid-base method to realize high yield comprises the following steps:
mixing graphite concentrate with concentrated sulfuric acid, and roasting at a low temperature to obtain sulfuric acid curing material;
mixing the sulfuric acid curing material with hydrochloric acid, leaching, and carrying out solid-liquid separation to obtain an acid leaching sample, wherein the acid leaching sample is washed to be neutral to obtain a solid to be treated;
carrying out first screening treatment on the solid to be treated, wherein the oversize is a high-carbon graphite product with a fixed carbon content of 94% -98%, and grinding, shaping and purifying the undersize to obtain high-purity spherical graphite;
or,
performing alkaline leaching on the solid to be treated, performing solid-liquid separation to obtain an alkaline leaching sample, washing the alkaline leaching sample to be neutral, performing second screening treatment, wherein the oversize product is a high-purity graphite product, and performing fine grinding, shaping and purification on the undersize product to obtain high-purity spherical graphite;
the graphite concentrate is the graphite concentrate with the water content less than or equal to 10% after the flotation of the graphite raw ore and drying at the temperature less than or equal to 100 ℃.
Preferably, the mass ratio of the concentrated sulfuric acid to the graphite concentrate is (0.5-1.2): 1.
preferably, the low-temperature roasting temperature is 150-350 ℃ and the time is 2-24h.
Preferably, the volume fraction of the hydrochloric acid is 1-10%;
the liquid-solid ratio of the leaching is (3-10) ml:1g, wherein the leaching temperature is 50-95 ℃ and the leaching time is 1-10h.
Preferably, the first sieving treatment uses a sieve having a pore size of 150 μm, 125 μm, 100 μm, 75 μm or 45 μm, or a combination of sieves of a plurality of different pore sizes in sequence.
Preferably, the alkaline leaching includes atmospheric alkaline leaching and pressurized alkaline leaching.
Preferably, the alkali leaching is atmospheric alkali leaching, in the atmospheric alkali leaching system, the concentration of sodium hydroxide is 100-300g/L, the temperature is 50-95 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-10h.
Preferably, the second sieving treatment uses a sieve with a pore size of 150 μm, 125 μm, 100 μm, 75 μm or 45 μm, and the oversize product has a fixed carbon content of not less than 99%.
Preferably, the alkali leaching is pressurized alkali leaching, and in a system of the pressurized alkali leaching, the concentration of sodium hydroxide is 100-300g/L, the temperature is 150-300 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-8h.
Preferably, the second sieving treatment uses a sieve with a pore size of 150 μm, 75 μm or 45 μm and a fixed carbon content of not less than 99.9% as the oversize material.
Compared with the prior art, the beneficial effects of this application include:
according to the method for purifying graphite by using the raw materials without high-temperature drying and by using a simple acid-base method, the raw materials do not need to be dried at high temperature, and the flotation residual medicament (one or more of a collector, a foaming agent, a regulator and an inhibitor) is combined with proper sulfuric acid curing and hydrochloric acid leaching, so that not only is the negative influence of the medicament eliminated, but also the granularity of solids can be increased in the purifying and leaching process (in the traditional process, along with the leaching, the granularity of solids is reduced), and the yield of oversize products is increased; and obtaining the high-purity graphite product which meets the national standard GB/T3518-2008 and has different fixed carbon contents through direct screening or alkaline leaching according to different product requirements.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a graph showing the particle size distribution of graphite concentrate after drying at 100deg.C;
FIG. 2 is a graph showing the particle size distribution of graphite concentrate after drying at 400 ℃;
FIG. 3 is a schematic process flow diagram of a method for purifying graphite by using a simple acid-base method without high-temperature drying of the raw materials provided in the embodiment;
FIG. 4 is a graph showing the particle size distribution of a 100℃oven-dried sample sulfuric acid cured material water sample obtained in comparative example 1;
FIG. 5 is a graph showing the particle size distribution of a 4% hydrochloric acid leaching sample obtained in example 1, which was dried at 100 ℃;
FIG. 6 is a graph showing the particle size distribution of a water sample of a sulfuric acid-cured material obtained in comparative example 2, which was baked at 400 ℃.
Detailed Description
In order to better explain the technical scheme provided by the application, before the embodiment, the technical scheme is integrally stated, and the technical scheme is specifically as follows:
a method for purifying graphite by a raw material high-temperature drying-free simple acid-base method to realize high yield comprises the following steps:
mixing graphite concentrate with concentrated sulfuric acid, and roasting at a low temperature to obtain sulfuric acid curing material;
mixing the sulfuric acid curing material with hydrochloric acid, leaching, and carrying out solid-liquid separation to obtain an acid leaching sample, wherein the acid leaching sample is washed to be neutral to obtain a solid to be treated;
carrying out first screening treatment on the solid to be treated, wherein the oversize is a high-carbon graphite product with a fixed carbon content of 94% -98%, and grinding, shaping and purifying the undersize to obtain high-purity spherical graphite;
or,
performing alkaline leaching on the solid to be treated, performing solid-liquid separation to obtain an alkaline leaching sample, washing the alkaline leaching sample to be neutral, performing second screening treatment, wherein the oversize product is a high-purity graphite product, and performing fine grinding, shaping and purification on the undersize product to obtain high-purity spherical graphite;
the graphite concentrate is the graphite concentrate with the water content less than or equal to 10% after the flotation of the graphite raw ore and drying at the temperature less than or equal to 100 ℃.
In an alternative embodiment, the mass ratio of the concentrated sulfuric acid to the graphite concentrate is (0.5-1.2): 1.
optionally, the mass ratio of the concentrated sulfuric acid to the graphite concentrate may be 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1.1: 1. 1.1: 1. 1.2:1 or (0.5-1.2): any value between 1.
In an alternative embodiment, the low temperature firing is at a temperature of 150 to 350 ℃ for a period of 2 to 24 hours.
Alternatively, the low temperature calcination may have a temperature of 150 ℃, 200 ℃, 250 ℃, 300 ℃, 350 ℃, or any value between 150 and 350 ℃, and the time may be any value between 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, or 2 to 24h.
In an alternative embodiment, the volume fraction of the hydrochloric acid is 1-10%;
the liquid-solid ratio of the leaching is (3-10) ml:1g, wherein the leaching temperature is 50-95 ℃ and the leaching time is 1-10h.
Alternatively, the volume fraction of hydrochloric acid may be any value between 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% or 1-10%; the leached liquid to solid ratio may be 3ml:1g, 4ml:1g, 5ml:1g, 6ml:1g, 7ml:1g, 8ml:1g, 9ml:1g, 10ml:1g or (3-10) ml: the leaching temperature can be any value between 1g, the leaching temperature can be any value between 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 50-95 ℃, and the leaching time can be any value between 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 1-10h.
In an alternative embodiment, the first screening process uses screens with a pore size of 150 μm, 125 μm, 100 μm, 75 μm or 45 μm, or a combination of screens in sequence of a plurality of different pore sizes.
In an alternative embodiment, the alkaline leaching includes atmospheric alkaline leaching and pressurized alkaline leaching.
In an alternative embodiment, the alkaline leaching is an atmospheric alkaline leaching system, wherein the concentration of sodium hydroxide is 100-300g/L, the temperature is 50-95 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-10h.
Optionally, in the system for atmospheric alkaline leaching, the concentration of sodium hydroxide may be any value between 100g/L, 150g/L, 200g/L, 250g/L, 300g/L or 100-300g/L, the temperature may be any value between 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 50-95 ℃, and the liquid-solid ratio may be 3ml:1g, 4ml:1g, 5ml:1g, 6ml:1g, 7ml:1g, 8ml:1g, 9ml:1g, 10ml:1g or (3-10) ml: the leaching time may be any value between 1g, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or any value between 1-10h.
In an alternative embodiment, the second sieving treatment uses a sieve with a pore size of 150 μm, 125 μm, 100 μm, 75 μm or 45 μm and a fixed carbon content of not less than 99%.
In an alternative embodiment, the alkaline leaching is a pressurized alkaline leaching system in which the sodium hydroxide concentration is 100-300g/L, the temperature is 150-300 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-8h.
Optionally, in the pressurized alkali leaching system, the concentration of sodium hydroxide may be any value between 100g/L, 150g/L, 200g/L, 250g/L, 300g/L or 100-300g/L, the temperature may be any value between 150 ℃, 200 ℃, 250 ℃, 300 ℃ or 150-300 ℃, and the liquid-solid ratio may be 3ml:1g, 4ml:1g, 5ml:1g, 6ml:1g, 7ml:1g, 8ml:1g, 9ml:1g, 10ml:1g or (3-10) ml: the leaching time may be any value between 1g, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h or any value between 1-8h.
In an alternative embodiment, the second sieving treatment uses a sieve with a pore size of 150 μm, 75 μm or 45 μm and a screen top with a fixed carbon content of not less than 99.9%.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
To illustrate the effect of drying temperature on the composition and particle size of the graphite concentrate after flotation, a control test was performed, specifically as follows:
the composition of the same batch of graphite concentrate after roasting at 100 ℃ (accurate metering, sample feeding analysis) and 400 ℃ was measured and the results are shown in table 1 below:
TABLE 1 analysis results of the components
As can be seen from Table 1, the volatile and sulfur contents in the graphite concentrate are obviously reduced at 400 ℃, but the fixed carbon content is not obviously changed, and the requirement of high-carbon graphite is not met (according to the requirements in national standard GB/T3518-2008, the fixed carbon content is 94 percent or less and less than 99.9 percent is high-carbon graphite, and the fixed carbon content is or more than 99.9 percent is high-purity graphite).
The particle size distribution diagram of the graphite concentrate after drying at 100 ℃ is shown in figure 1; the particle size distribution diagram of the graphite concentrate after drying at 400 ℃ is shown in figure 2. Comparing fig. 1 and fig. 2, it was found that the particle size d (0.5) 66.411 μm of the graphite concentrate obtained by drying at 400 ℃ was significantly larger than the particle size d (0.5) 51.40 μm of the graphite concentrate obtained by drying at 100 ℃.
The following examples all used graphite concentrate obtained by drying at 100 ℃ as raw material (laboratory for accurate metering, and for drying of the material).
Example 1
As shown in fig. 3, the embodiment provides a method for purifying graphite by using a simple acid-base method to realize high yield without high-temperature drying of raw materials, which specifically comprises the following steps:
step 1: graphite concentrate (less than or equal to 10 percent of water) and concentrated sulfuric acid are mixed according to an acid-mineral ratio (mass ratio) of 1: and 0.8, mixing and stirring to realize the effect of uniform infiltration of graphite concentrate and sulfuric acid.
Step 2: roasting the soaked sample of the graphite concentrate and sulfuric acid obtained in the step 1 at 200 ℃ for 20 hours to obtain a sulfuric acid curing material.
Step 3: and (3) stirring and leaching the sulfuric acid cured material obtained in the step (2) and a 4% hydrochloric acid solution, wherein the leaching temperature is 80 ℃, the liquid-solid ratio is 8:1, and the leaching time is 2h. Filtering and separating solid from liquid to obtain an acid leaching sample and an acid leaching liquid. The acid leaching sample is washed to be neutral by deionized water. FIG. 5 is a graph showing the particle size distribution of a 4% hydrochloric acid leaching sample obtained in example 1, which was dried at 100 ℃.
Step 4: and (3) washing the neutral acid leaching sample obtained in the step (3) to carry out screening treatment of 45 mu m, analyzing the obtained oversize product, wherein the volatile content is 1.1%, the moisture content is 0.47%, and the fixed carbon content is 96.5%, so that the product meets the product brand of LG (-) 45-96.
Grinding, shaping and purifying the undersize to obtain the high-purity spherical graphite.
Comparative example 1
Unlike example 1, in step 3, the 4% hydrochloric acid solution was replaced with an equal amount of deionized water.
The sulfuric acid-cured stock water samples obtained in comparative example 1 and the 4% hydrochloric acid-leached samples obtained in example 1 had fixed carbon contents of 95.47% and 96.02%, respectively. The particle size distribution was as in FIG. 4 (water leaching) and FIG. 5 (4% hydrochloric acid leaching), with particle sizes increased to d (0.5) 60.147 μm and d (0.5) 73.475 μm, respectively. The comparison shows that the hydrochloric acid is leached after the sulfuric acid is adopted for curing, the fixed carbon and the granularity are obviously increased compared with water leaching, and the tendency of preparing more national standard products can be improved.
Specific: the graphite concentrate raw material has 56.58% of 45 μm oversize, 62.22% of water leaching sample oversize and 71.16% of acid leaching sample oversize.
Comparative example 2
Unlike example 1, in step 1, graphite concentrate obtained under the condition of roasting at 400 ℃ was used as a raw material. In step 3, the 4% hydrochloric acid solution was replaced with an equal amount of deionized water.
The sulfuric acid-cured material obtained in comparative example 2 was water-leached (particle size distribution shown in FIG. 6) and the water-leached material obtained in comparative example 1 were each 95.05% and 95.47% in fixed carbon content. Particle size distribution plot 4 (100 ℃ C. Water immersion sample) compared to FIG. 6 (400 ℃ C. Water immersion sample), particle size increased from d (0.5) 51.4 μm to d (0.5) 60.147 μm, whereas 400 ℃ C. Sample, particle size decreased from d (0.5) 66.411 μm to d (0.5) 61.274 μm. The fixed carbon content of the sample at 400 ℃ is reduced relative to the sample at 100 ℃, and the method accords with the rules of coarse granularity of the initial raw materials and poor impurity removal effect of chemical reaction. The sample at 400 ℃ also accords with the rule of reducing the granularity after chemical treatment compared with the initial granularity.
Example 2
The embodiment provides a method for purifying graphite by using a simple acid-base method and without high-temperature drying of raw materials, which specifically comprises the following steps:
step 1: graphite concentrate (less than or equal to 10 percent of water) and concentrated sulfuric acid are mixed according to an acid-mineral ratio (mass ratio) of 1: and 0.7, mixing and stirring to realize the effect of uniform infiltration of graphite concentrate and sulfuric acid.
Step 2: roasting the soaked sample of the graphite concentrate and sulfuric acid obtained in the step 1 at 300 ℃ for 6 hours to obtain a sulfuric acid curing material.
Step 3: and (3) stirring and leaching the sulfuric acid cured material obtained in the step (2) and a 6% hydrochloric acid solution, wherein the leaching temperature is 80 ℃, the liquid-solid ratio is 4:1, and the leaching time is 3h. Filtering and separating solid from liquid to obtain an acid leaching sample and an acid leaching liquid. The acid leaching sample is washed to be neutral by deionized water.
Step 4: and (3) washing the neutral acid leaching sample obtained in the step (3) to carry out 150 mu m screening treatment, analyzing the obtained oversize product, wherein the volatile content is 0.9%, the moisture content is 0.45%, and the fixed carbon content is 98.2%, so that the product meets the product brand of LG (-) 150-98.
Grinding, shaping and purifying the undersize to obtain the high-purity spherical graphite.
Example 3
The embodiment provides a method for purifying graphite by using a simple acid-base method and without high-temperature drying of raw materials, which specifically comprises the following steps:
step 1: graphite concentrate (less than or equal to 10 percent of water) and concentrated sulfuric acid are mixed according to an acid-mineral ratio (mass ratio) of 1: and 0.6, mixing and stirring to realize the effect of uniform infiltration of graphite concentrate and sulfuric acid.
Step 2: roasting the soaked sample of the graphite concentrate and sulfuric acid obtained in the step 1 at 320 ℃ for 12 hours to obtain a sulfuric acid curing material.
Step 3: and (3) stirring and leaching the sulfuric acid cured material obtained in the step (2) and 8% hydrochloric acid solution, wherein the leaching temperature is 70 ℃, the liquid-solid ratio is 6:1, and the leaching time is 6h. Filtering and separating solid from liquid to obtain an acid leaching sample and an acid leaching liquid. The acid leaching sample is washed to be neutral by deionized water.
Step 4: and (3) washing the acid leaching sample which is neutral in the step (3) to perform normal-pressure alkaline leaching, wherein the concentration of NaOH is 250g/l, the leaching temperature is 90 ℃, the liquid-solid ratio is 6:1, and the leaching time is 6h. Filtering and separating solid from liquid to obtain normal pressure alkaline leaching sample and alkaline leaching liquid. The alkaline leaching sample is washed to be neutral by deionized water.
Step 5: and (3) washing the neutral normal-pressure alkaline leaching sample obtained in the step (4) to perform 100um screening treatment, analyzing the obtained oversize product, wherein the volatile content is 0.6%, the moisture content is 0.3%, and the fixed carbon content is 99.3%, so that the product meets the high-carbon graphite product of LG (-) 100-99 product brand.
Grinding, shaping and purifying the undersize to obtain the high-purity spherical graphite.
Example 4
The embodiment provides a method for purifying graphite by using a simple acid-base method and without high-temperature drying of raw materials, which specifically comprises the following steps:
step 1: mixing and stirring graphite concentrate (less than or equal to 10% of water) and concentrated sulfuric acid according to an acid-ore ratio (mass ratio) of 1.0, so as to realize the effect of uniformly soaking the graphite concentrate and the sulfuric acid.
Step 2: roasting the soaked sample of the graphite concentrate and sulfuric acid obtained in the step 1 at 330 ℃ for 8 hours to obtain a sulfuric acid curing material.
Step 3: and (3) stirring and leaching the sulfuric acid cured material obtained in the step (2) and a 4% hydrochloric acid solution, wherein the leaching temperature is 90 ℃, the liquid-solid ratio is 8:1, and the leaching time is 8h. Filtering and separating solid from liquid to obtain an acid leaching sample and an acid leaching liquid. The acid leaching sample is washed to be neutral by deionized water.
Step 4: and (3) washing the acid leaching sample which is neutral in the step (3) to carry out pressurized alkali leaching, wherein the concentration of NaOH is 250g/l, the leaching temperature is 220 ℃, the liquid-solid ratio is 8:1, and the leaching time is 4h. Filtering and separating solid from liquid to obtain a pressurized alkaline leaching sample and an alkaline leaching liquid. The alkaline leaching sample is washed to be neutral by deionized water.
Step 5: and (3) washing the neutral pressurized alkaline leaching sample obtained in the step (4) to perform 75um screening treatment, analyzing the obtained oversize product, wherein the water content is 0.14%, the fixed carbon content is 99.92%, and the product meets the product brand of LG (-) 75-99.9.
Grinding, shaping and purifying the undersize to obtain the high-purity spherical graphite.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Claims (10)
1. The method for purifying graphite by using a simple acid-base method to realize high yield without high-temperature drying of raw materials is characterized by comprising the following steps:
mixing graphite concentrate with concentrated sulfuric acid, and roasting at a low temperature to obtain sulfuric acid curing material;
mixing the sulfuric acid curing material with hydrochloric acid, leaching, and carrying out solid-liquid separation to obtain an acid leaching sample, wherein the acid leaching sample is washed to be neutral to obtain a solid to be treated;
carrying out first screening treatment on the solid to be treated, wherein the oversize is a high-carbon graphite product with a fixed carbon content of 94% -98%, and grinding, shaping and purifying the undersize to obtain high-purity spherical graphite;
or,
performing alkaline leaching on the solid to be treated, performing solid-liquid separation to obtain an alkaline leaching sample, washing the alkaline leaching sample to be neutral, performing second screening treatment, wherein the oversize product is a high-purity graphite product, and performing fine grinding, shaping and purification on the undersize product to obtain high-purity spherical graphite;
the graphite concentrate is the graphite concentrate with the water content less than or equal to 10% after the flotation of the graphite raw ore and drying at the temperature less than or equal to 100 ℃.
2. The method for purifying graphite by using a simple acid-base method to realize high yield without high-temperature drying of raw materials according to claim 1, wherein the mass ratio of the concentrated sulfuric acid to the graphite concentrate is (0.5-1.2): 1.
3. the method for purifying graphite by using the simple acid-base method to realize high yield without high-temperature drying of raw materials according to claim 1, wherein the low-temperature roasting temperature is 150-350 ℃ and the time is 2-24h.
4. The method for purifying graphite by using the raw material free of high-temperature drying and adopting a simple acid-base method to realize high yield is characterized in that the volume fraction of hydrochloric acid is 1-10%;
the liquid-solid ratio of the leaching is (3-10) ml:1g, wherein the leaching temperature is 50-95 ℃ and the leaching time is 1-10h.
5. The method for purifying graphite with high yield by using the simple acid-base method without high temperature drying of raw materials according to claim 1, wherein the mesh size of the screen used in the first screening treatment is 150 μm, 125 μm, 100 μm, 75 μm or 45 μm, or a combination of screens with a plurality of different pore sizes is sequentially screened.
6. The method for high-yield purified graphite by using a simple acid-base method without high-temperature drying of raw materials according to any one of claims 1 to 5, wherein the alkaline leaching comprises normal-pressure alkaline leaching and pressure alkaline leaching.
7. The method for purifying graphite by using the simple acid-base method to realize high yield without high-temperature drying of raw materials according to claim 6, wherein the alkaline leaching is normal pressure alkaline leaching, in a system of the normal pressure alkaline leaching, the concentration of sodium hydroxide is 100-300g/L, the temperature is 50-95 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-10h.
8. The method for purifying graphite with high yield by using the simple acid-base method without high temperature drying of raw materials according to claim 7, wherein the pore diameter of the screen used in the second screening treatment is 150 μm, 125 μm, 100 μm, 75 μm or 45 μm, and the content of the oversize is not less than 99% of the fixed carbon.
9. The method for purifying graphite by using a simple acid-base method to realize high yield without high-temperature drying of raw materials according to claim 6, wherein the alkaline leaching is pressure alkaline leaching, the concentration of sodium hydroxide in a pressure alkaline leaching system is 100-300g/L, the temperature is 150-300 ℃, and the liquid-solid ratio is (3-10) ml:1g, leaching time is 1-8h.
10. The method for purifying graphite with high yield by using the simple acid-base method without high temperature drying of raw materials according to claim 9, wherein the pore diameter of the screen used in the second screening treatment is 150 μm, 75 μm or 45 μm, and the content of the oversize material is not less than 99.9% of the fixed carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410238826.5A CN117819541B (en) | 2024-03-04 | 2024-03-04 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410238826.5A CN117819541B (en) | 2024-03-04 | 2024-03-04 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117819541A true CN117819541A (en) | 2024-04-05 |
| CN117819541B CN117819541B (en) | 2024-06-04 |
Family
ID=90521249
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410238826.5A Active CN117819541B (en) | 2024-03-04 | 2024-03-04 | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117819541B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973545A (en) * | 2010-11-08 | 2011-02-16 | 昆明冶金研究院 | Method for purifying high-purity graphite |
| CN104098092A (en) * | 2014-08-03 | 2014-10-15 | 北京矿冶研究总院 | Method for purifying natural microcrystalline graphite |
| CN107462452A (en) * | 2017-09-25 | 2017-12-12 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method for determining crystalline flake graphite ore deposit particle size distribution characteristics |
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN107555428A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite secondary pickling method of purification and its high-purity micro crystal graphite |
| CN207418305U (en) * | 2017-10-31 | 2018-05-29 | 湖南国盛石墨科技有限公司 | A kind of high-purity micro crystal graphite production system |
| CN110745820A (en) * | 2019-12-04 | 2020-02-04 | 辽宁工程技术大学 | Purification method of smokeless coal-based microcrystalline graphite for preparing lithium ion battery negative electrode material |
| CN110828926A (en) * | 2019-09-26 | 2020-02-21 | 北京矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| CN110835682A (en) * | 2019-09-26 | 2020-02-25 | 北京矿冶科技集团有限公司 | Method for cooperatively treating positive and negative active materials of waste lithium ion battery |
| CN112794322A (en) * | 2020-12-28 | 2021-05-14 | 萝北奥星新材料有限公司 | Purification method of graphite |
| CN117550594A (en) * | 2023-12-29 | 2024-02-13 | 苏州中材非金属矿工业设计研究院有限公司 | Purification method of high-purity graphite |
-
2024
- 2024-03-04 CN CN202410238826.5A patent/CN117819541B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101973545A (en) * | 2010-11-08 | 2011-02-16 | 昆明冶金研究院 | Method for purifying high-purity graphite |
| CN104098092A (en) * | 2014-08-03 | 2014-10-15 | 北京矿冶研究总院 | Method for purifying natural microcrystalline graphite |
| CN107462452A (en) * | 2017-09-25 | 2017-12-12 | 苏州中材非金属矿工业设计研究院有限公司 | A kind of method for determining crystalline flake graphite ore deposit particle size distribution characteristics |
| CN107555425A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite high temperature pre-processes alkali acid system method of purification |
| CN107555428A (en) * | 2017-10-31 | 2018-01-09 | 湖南国盛石墨科技有限公司 | A kind of micro crystal graphite secondary pickling method of purification and its high-purity micro crystal graphite |
| CN207418305U (en) * | 2017-10-31 | 2018-05-29 | 湖南国盛石墨科技有限公司 | A kind of high-purity micro crystal graphite production system |
| CN110828926A (en) * | 2019-09-26 | 2020-02-21 | 北京矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| CN110835682A (en) * | 2019-09-26 | 2020-02-25 | 北京矿冶科技集团有限公司 | Method for cooperatively treating positive and negative active materials of waste lithium ion battery |
| CN110745820A (en) * | 2019-12-04 | 2020-02-04 | 辽宁工程技术大学 | Purification method of smokeless coal-based microcrystalline graphite for preparing lithium ion battery negative electrode material |
| CN112794322A (en) * | 2020-12-28 | 2021-05-14 | 萝北奥星新材料有限公司 | Purification method of graphite |
| CN117550594A (en) * | 2023-12-29 | 2024-02-13 | 苏州中材非金属矿工业设计研究院有限公司 | Purification method of high-purity graphite |
Non-Patent Citations (2)
| Title |
|---|
| 周开洪等: ""隐晶质石墨浮选初步研究"", 《矿业研究与开发》, vol. 32, no. 4, 31 August 2012 (2012-08-31), pages 58 - 59 * |
| 葛鹏;王化军;赵晶;解琳;张强;: "碱酸法石墨提纯效果的制约因素", 金属矿山, no. 05, 15 May 2010 (2010-05-15), pages 96 - 98 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117819541B (en) | 2024-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106587116B (en) | A kind of method for extracting lithium carbonate and aluminium hydroxide using lepidolite and flyash | |
| CN102674460B (en) | Preparation method for high-purity ammonium paratungstate | |
| CN110885090A (en) | Method for preparing battery-grade lithium carbonate by using lepidolite as raw material through one-step method | |
| CN105289837A (en) | Process adopting barite-fluorite paragenic ore for preparing barite powder | |
| CN102071323B (en) | Method for producing high-purity gold by utilizing electroplating waste liquid containing gold | |
| CN111129635A (en) | Method and device for separating anode material and cathode material of waste lithium battery | |
| CN113716559A (en) | Strong acid method scale graphite purification process and device | |
| CN110294473B (en) | Preparation process for purifying microcrystalline graphite by organic acid catalysis | |
| CN101148268A (en) | Method for separating and extracting calcium tungstate and tin slag by utilizing tungsten-containing tin furnace residue or tungsten-tin middlings | |
| CN117819541B (en) | Method for purifying graphite by high-temperature drying-free raw materials and simple acid-base method | |
| Zheng et al. | Industrial experiment of copper electrolyte purification by copper arsenite | |
| CN108950181A (en) | A kind of preparation process of beryllium oxide | |
| CN112063837A (en) | Method and system for rapid gravity settling of slurry | |
| LIU et al. | Optimization of separation processing of copper and iron of dump bioleaching solution by Lix 984N in Dexing Copper Mine | |
| CN108609661B (en) | Method for preparing iron oxide red, aluminum oxide and gallium by using iron-removing resin eluent | |
| Mazurek et al. | Method of utilization of the spent vanadium catalyst | |
| TWI705142B (en) | Method for recycling silver and tantalum from waste tantalum capacitors | |
| CN105861843A (en) | Efficient method for enriching rhenium from high-arsenic copper sulfide material containing rhenium | |
| CN103011284B (en) | Method for removing impurities from crude bismuth oxide | |
| CN103028483B (en) | Method for preparing high-purity gold-loaded pyrite for experiments | |
| CN103882237A (en) | Production process for leaching of cobalt from cobalt-containing water-quenched slag | |
| CN102992401B (en) | Process for producing bismuth aluminate by using crude bismuth oxide | |
| CN111302394B (en) | Regeneration method of deep purification agent used in production of alumina by one-step acid dissolution method | |
| CN103011285B (en) | Process for producing pentahydrate bismuth nitrate by employing crude bismuth oxide | |
| CN113800566B (en) | Method for preparing ammonium molybdate from crude molybdic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |